Note: Descriptions are shown in the official language in which they were submitted.
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DETERGENT COMPOSITIONS IN TABLET FORM
Field of the Invention
The present invention relates to detergent compositions in tablet
form having an improved hardness profile.
Background of the Invention
The traditional form of detergent compositions for use in
automatic dishwashing or laundry machines is granular or particulate.
Such compositions are measured and dosed by the consumer and
placed in the dispenser of the machine which is located in the door in
the case of dishwashing machines or the dispensing tray of an
automatic laundry washing machine.
In order to simplify the dosing of detergents for automatic
washing machines however, many of the automatic washing detergent
compositions are now provided in the form of non particulate solids
such as bars or tablets or briquettes. This. provides a number of
advantages to both the consumer and manufacturer. Firstly, such
tablets prevent spillage of the detergent composition. Secondly, the
tablets eliminate the need for the consumer to estimate the dosage of
detergent composition required and ensure that the correct dosage of
detergent composition per wash is used by the consumer. Thirdly, the
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use of ~ tablets minimises the contact by the consumer with the
composition.
However, there are a number of problems associated with the
use of tablets. In order to provide optimum performance benefits the
tablets require a certain dissolution profile during the programme cycle
of the machine.
In addition, it is also highly desirable that the tablets to possess a
certain degree of hardness or tablet strength. In particular the tablets
should be sufficiently hard to meet safety requirements. Tabletted
detergent compositions are typically highly alkaline and thus oral
consumption must be avoided. However, tablets often appear attractive
to children, who may attempt to consume them.
Furthermore, it is also desirable that the tablets should be hard
enough so that they preferably do not deteriorate, lose their structure
or decompose upon packing, transport or storage.
Background Art
Detergent tablets and methods of their preparation are known in
the art. For example WO 94/23011 discloses stable, bifunctional
phosphate-, metasilicate- and polymer free, low alkaline cleaning agent
tablet for dishwashing machines. The composition may comprise from
1-60% anhydrous sodium carbonate, 0-60% sodium disilicate and 3-
10% water.
WO 93/00419 discloses a process for producing phosphate and
metasilicate free, low alkaline cleaning agent tablets for machine
dishwashing. The tablets consist of solid alkali salts of at least one
polymer of acrylic acid and builders including anhydrous sodium
carbonate. The tablets may comprise anhydrous sodium disilicate. The
carbonate undergoes mixing alone or together with other builders and
the polymer and with from 5-40 % water to result in the partial
hydration of the carbonate. The remaining components are then added
and compressed into tablet form.
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WO 91/15568 discloses stable, phosphate free detergent tablets
for use in dishwashing machines containing anhydrous meta silicate,
nonionics, builders, bleach, 35-60 % acrylic polymers, 25-50
anhydrous carbonate, 4-20 % anhydrous sodium sulphate and 1-7
water. The tablets are prepared by compression such that they have a
flexural strength of at least 120N.
EPO 481 792 discloses detergent compositions in tablet form
comprising a persalt, bleach activator and S-80 % detergent builders,
polymers (0.5-15 % ), alkali metal silicates (0.1 %-10% ), carbonate and
sulphate (not disclosed as anhydrous). Water is not disclosed in the
description but the exemplified tablet composition comprises 13.5-
16.5 % moisture in addition to carbonate, alkaline silicate and polymer:
The tablets are prepared by compression of the premixed composition.
EPO 170 791 discloses a process for making a washing
composition in tablet form. The process consists of granulating bleach
activator, nonionic surfactants, quaternary ammonium compounds,
fatty amine derivatives and aminopropanionic acid derivatives with
tabletting aids and spraying the granulate with a liquid builder and
drying to a water content of at most 6% and compressing into tablets.
All of the identified prior art documents disclose means of
increasing tablet hardness using compression of the granular detergent
composition following pretreatment of the granular composition
ingredients. It is thus an aim of the present invention to provide a
tabletted detergent composition having increased strength without
substantially increasing the compression force.
It is a further aim of the present invention to provide a tablet
having increased strength and hardness with minimal adaptation of the
compression manufacturing process, particularly with respect to the
tooling required for compression of the detergent composition into
tablets.
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It is a further aim of the present invention to provide a tabletted
detergent composition having the desired dissolution profile.
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Summary of the Invention
The present invention is a carbonate free tabletted detergent
composition comprising from 45 % to 80 % of a hydratable builder
system, wherein said builder is not fully hydrated and
from 5 % to 30 % total water content, wherein said total water
content comprises water derived from said builder system, optional
ingredients and from added water, wherein the ratio of said total water
content to added water content is from 100:1 to 5:4.
All amounts, weights, ratios and percentages are as a % weight of
the detergent composition unless otherwise stated.
Detailed Description of the Invention
Thus, according to the present invention the detergent
composition is in a tabletted form. As used herein the term tabletted
refers to a non-particulate solid, which may be a bar, briquette, cake
or tablet. The tabletted detergent composition of the present invention
is a carbonate free composition comprising as essential ingredients a
non fully hydrated builder system and water.
Builder system
The carbonate free tabletted detergent composition of the present
invention comprises as an essential component from 45 % to 80 % ,
preferably from 65 % to 75 % of a detergency builder system. Said
builder is not fully hydrated and is preferably less than SO % hydrated,
more preferably less than 30 % hydrated, most preferably less than
28 % hydrated. As used herein the term fully hydrated builder refers to
builders in which all the vacant co-ordination sites are occupied by
water molecules. Suitable builders for use herein are described herein
below. The builder may comprise essentially of only one builder
component or a number of builder components. The degree of
hydration of each of said components is independent of one another
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such that the overall hydration of the builder is the mean value of all of
the builder components present in the detergent composition.
According to the present invention suitable builders for use in the
present invention include inorganic or P-containing detergent builders
including the alkali metal, ammonium and alkanolammonium salts of
polyphosphates (exemplified by the tripolyphosphates, pyrophosphates,
and glassy polymeric meta-phosphates), phosphonates, phytic acid,
silicates, aluminosilicates and builder/fillers such as sulphates.
However, non-phosphate builders are required in some locales.
Importantly, the compositions herein function surprisingly well even in
the presence of the so-called "weak" builders (as compared with
phosphates) such as citrate, or in the so-called "underbuilt" situation
that may occur with zeolite or layered silicate builders.
Examples of silicate builders are the alkali metal silicates,
particularly those having a Si02:Na20 ratio in the range 1.6:1 to 3.2:1
and layered silicates, such as the layered sodium silicates described in
U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-6
is the trademark for a crystalline layered silicate marketed by Hoechst
(commonly abbreviated herein as "SKS-6"). Unlike zeolite builders,
the Na SKS-6 silicate builder does not contain aluminium. NaSKS-6
has the delta-Na2Si05 morphology form of layered silicate. It can be
prepared by methods such as those described in German DE-A-
3,417,649 and DE-A-3,742,043. SKS-6 is a highly preferred layered
silicate for use herein, but other such layered silicates, such as those
having the general formula NaMSi~02x+1'YH20 Wherein M is
sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y
is a number from 0 to 20, preferably 0 can be used herein. Various
other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and
NaSKS-11, as the alpha, beta and gamma forms. As noted above, the
delta-Na2Si05 (NaSKS-6 form) is most preferred for use herein. Other
silicates may also be useful such as for example magnesium silicate,
which can serve as a crispening agent in granular formulations, as a
stabilizing agent for oxygen bleaches, and as a component of suds
control systems.
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Aluminosilicate builders are useful in the present invention.
Aluminosilicate builders are of great importance in most currently
marketed heavy duty granular detergent compositions. Aluminosilicate
builders include those having the empirical formula:
Mz(zA102)y] . xH20
wherein z and y are integers of at least 6, the molar ratio of z to y
is in the range from 1.0 to about 0.5, and x is an integer from about 15
to about 264.
Useful aluminosilicate ion exchange materials are commercially
available. These aluminosilicates can be crystalline or amorphous in
structure and can be naturally-occurring aluminosilicates or
synthetically derived. A method for producing aluminosilicate ion
exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et
al, issued October 12, 1976. Preferred synthetic crystalline
aluminosilicate ion exchange materials useful herein are available
under the designations Zeolite A, Zeolite P (B), Zeolite MAP and
Zeolite X. In an especially preferred embodiment, the crystalline
aluminosilicate ion exchange material has the formula:
Nal2~(A102) 12(Si02) 12] ~ xH20
wherein x is from about 20 to about 30, especially about 27. This
material is known as Zeolite A. Dehydrated zeolites (x = 0 - 10) may
also be used herein. Preferably, the aluminosilicate has a particle size
of about 0.1-10 microns in diameter.
Organic detergent builders suitable for the purposes of the present
invention include, but are not restricted to, a wide variety of
polycarboxylate compounds. As used herein, "polycarboxylate" refers
to compounds having a plurality of carboxylate groups, preferably at
least 3 carboxylates. Polycarboxylate builder can generally be added to
the composition in acid form, but can also be added in the form of a
neutralized salt. When utilised in salt form, alkali metals, such as
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sodium, potassium, and lithium, or alkanolammonium salts are
preferred.
Included among the polycarboxylate builders are a variety of
categories of useful materials. One important category of
polycarboxylate builders encompasses the ether polycarboxylates,
including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287,
issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830,
issued January 18, 1972. See also "TMS/TDS" builders of U.S.
Patent 4,663,071, issued to Bush et al, on May 5, 1987. Suitable ether
polycarboxylates also include cyclic compounds, particularly alicyclic
compounds, such as those described in U.S. Patents 3,923,679;
3,835,163; 4,158,635; 4,120,874 and 4,102,903.
Other useful detergency builders include the ether
hydroxypolycarboxylates, copolymers of malefic anhydride with
ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-
trisulphonic acid, and carboxymethyloxysuccinic acid, the various
alkali metal, ammonium and substituted ammonium salts of polyacetic
acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid,
as well as polycarboxylates such as mellitic acid, succinic acid,
oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,
carboRymethyloxysuccinic acid, and soluble salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof
(particularly sodium salt), are polycarboxylate builders of particular
importance. Citrates may be used in granular compositions, especially
in combination with zeolite and/or layered silicate builders.
Oxydisuccinates are also especially useful in such compositions and
combinations.
Also suitable in the detergent compositions of the present
invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the
related compounds disclosed in U.S. Patent 4,566,984, Bush, issued
January 2,8, 1986. Useful succinic acid builders include the CS-C20
alkyl and alkenyl succinic acids and salts thereof. A particularly
preferred compound of this type is dodecenylsuccinic acid. Specific
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examples of succinate builders include: laurylsuccinate,
myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred),
2-pentadecenylsuccinate, and the like. Laurylsuccinates are the
preferred builders of this group, and are described in European Patent
Application 86200690.5/0,200,263, published November 5, 1986.
Other suitable polycarboxylates are disclosed in U.S. Patent
4,144,226, Crutchfield et al, issued March 13, 1979 and in U.S. Patent
3,308,067, Diehl, issued March 7, 1967. See also Diehl U.S. Patent
3,723,322.
Fatty acids, e.g. , C 12-C 1 g monocarboxylic acids, can also be
incorporated into the compositions alone, or in combination with the
aforesaid builders, especially citrate and/or the succinate builders, to
provide additional builder activity. Such use of fatty acids will
generally result in a diminution of sudsing, which should be taken into
account by the formulator.
In situations where phosphorus-based builders can be used, the
various alkali metal phosphates such as the well-known sodium
tripolyphosphates, sodium pyrophosphate and sodium orthophosphate
can be used. Phosphonate builders such as ethane-1-hydroxy-1,1-
diphosphonate and other known phosphonates (see, for example, U.S.
Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137)
can also be used.
The tabletted detergent composition of the present invention
preferably comprises builders selected from sulphates, phosphates,
silicates and mixtures thereof. More preferably the builders are
selected in order of preference from silicate, sulphate, citrate, and
mixtures thereof.
Water
According to the present invention the tabletted detergent
compositions also comprise as an essential ingredient from 5 % to
30 % , preferably from 5 % to 20 % , most preferably from 10 % to 15
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of watei. The water content of the tabletted detergent composition of
the present invention may be determined by methods known and
described in the art, such as distillation methods. Such methods
determine the total water content i.e. mobile/free water and bound
water present in the tablet.
Whilst not wishing to be bound by theory, it is believed that the
ratio of free and bound water present in the tablet contributes to the
hardness of the tablet. This ratio of free and bound water may be
measured in terms of percentage equilibrium relative humidity or
detection water. Preferably, the percentage equilibrium relative
humidity is from 29 % to 50 % , preferably from 30 % to 40 % , more
preferably from 30 % to 38 % , most preferably from 30 % to 35 % at 26
°C. The water present in the tablet is mainly derived from the tablet
ingredients themselves such as from the builder system. However, it
has been found that in order to achieve the optimal ratio of free/mobile
and bound water, water must be added by the formulator. Thus, it is
an essential feature of the present invention that additional water is
added to the detergent formulation, preferably prior to compression.
Alternatively, the additional water was be added to the detergent
composition prior to tabletting by exposing the composition to a
controlled humid environment. Preferably the tabletted detergent
composition comprises from 0.3 % to 4 % , more preferably from 0.3
to 3 % , most preferably from 0.3 % to 1 % of water by weight of the
total detergent composition is added by the formulator and is not
derived from the components of the tabletted composition. According
to the present invention the ratio of total water content of the tabletted
composition to added water is in the ratio of from 100:1 to 5:4,
preferably 70:1 to 5:3, more preferably from 50:1 to 15:1.
Adj unct Ingredients
The compositions herein can optionally include one or more other
detergent adjunct materials or other materials for assisting or
enhancing cleaning performance, treatment of the substrate to be
cleaned, or to modify the aesthetics of the detergent composition (e.g.,
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perfumes, colorants, dyes, etc.). The following are illustrative
examples of such adjunct materials.
Detersive Surfacta_n c
Nonlimiting examples of surfactants useful herein typically at
levels from about 1 % to about 55 9f , by weight, include the
conventional C 11-C 1 g alkyl benzene sulfonates ("LAS") and primary,
branched-chain and random C 1 p-C2p alkyl sulphates ("AS"), the
C 1 p-C 1 g secondary (2,3) alkyl sulphates of the formula
CH3(CH~x(CHOS03-M +) CH3 and CH3 (CH2)y(CHOS03-M +)
CH2CH3 where x and (y + 1 ) are integers of at least about 7,
.preferably at least about 9, and M is a water-solubilizing cation,
especially sodium, unsaturated sulphates such as oleoyl sulphate, the
Clp-Clg alkyl alkoxy sulphates ("AExS"; especially EO 1-7 ethoxy
sulphates), C 1 p-C 1 g alkyl alkoxy carboxylates (especially the EO 1-5
ethoxycarboxylates), the C 1 ~ 1 g glycerol ethers, the C 1 p-C 1 g alkyl
polyglycosides and their corresponding sulphated polyglycosides, and
C 12-C 1 g alpha- fatty acid esters. If desired, the conventional nonionic
and amphoteric surfactants such as the C 12-C 1 g alkyl ethoxylates
("AE°) including the so-called narrow peaked alkyl ethoxylates and
C6-C 12 alkyl phenol alkoxylates (especially ethoxylates and mixed
ethoxy/propoxy), C 12-C 1 g betaines and sulfobetaines ("sultaines"),
C lp-C 1 g amine oxides, and the tike, can also be included in the
overall compositions. The C 1 p-C 1 g N-alkyl polyhydroxy fatty ac id
amides caa also be used. Typical examples include the C 12-C 1 g N-
methylglucamides. See WO 9,206,154. Other sugar-derived
surfactants include the N-alkoxy polyhydroxy fatty acid amides, such
as C 1 p-C 1 g N-(3-methoxypropyl) glucamide. The N-propyl through
N-hexyl C 12-C 1 g glucamides can be used for low sudsing. C l p-C20
conventional soaps may also be used. Mixtures of anionic and
nonionic surfactants are especially useful. Other conventional useful
surfactants are listed in standard texts.
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Polymeric Dispensing Agents
Polymeric dispersing agents can advantageously be utilised at
levels from about 0. I % to about 7 % , by weight, in the compositions
herein, especially in the presence of zeolite and/or layered silicate
builders. Suitable polymeric dispersing agents include polyethylene
glycols PEG, although others known in the art can also be used. It is
believed, though it is not intended to be limited by theory, that
polymeric dispersing agents enhance overall detergent builder
performance, when used in combination with other builders (including
lower molecular weight polycarboxylates) by crystal growth inhibition,
particulate soil release peptization, and anti-redeposition.
PEG can exhibit dispersing agent performance as well as act as a
clay soil removal-antiredeposition agent. Typical molecular weight
ranges for these purposes range from about 500 to about 100,000;
preferably from about 1,000 to about 50,000, more preferably from
about 1,500 to about 10,000.
Polyaspartate and polyglutamate dispersing agents may also be
used, especially in conjunction with zeolite builders. Dispersing agents
such as polyaspartate preferably have a molecular weight (avg.) of
about 10,000.
Polymeric Polycarboxylates
According to the present invention another optimal component is a
polymeric polycarboxylate.
Said polymeric polycarboxylate is present at from 1 % to 30 9f ,
preferably from 196 to 10%, more preferably from 1 % to 5 ~6.
Polymeric polycarboxylate materials can be prepared by
polymerizing or copolymerizing suitable unsaturated monomers,
preferably in their acid form. Unsaturated monomeric acids that can
be polymerized to form suitable polymeric polycarboxylates include
acrylic acid, malefic acid (or malefic anhydride), fumaric acid, itaconic
acid, aconitic acid, mesaconic acid, citraconic acid and
methylenemalonic acid. The presence in the polymeric
polycarboxylates herein or monomeric segments, containing no
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carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc.
is suitable provided that such segments do not constitute more than
about 40% by weight.
Particularly suitable polymeric polycarboxylates can be derived
from acrylic acid. Such acrylic acid-based polymers which are useful
herein are the water-soluble salts of polymerized acrylic acid. The
average molecular weight of such polymers in the acid form preferably
ranges from about 2,000 to 10,000, more preferably from about 4,000
to 7,000 and most preferably from about 4,000 to 5,000. Water-soluble
salts of such acrylic acid polymers can include, for example, the alkali
metal, ammonium and substituted ammonium salts. Soluble polymers
of this type are known materials. Use of polyacrylates of this type in
detergent compositions has been disclosed, for example, in Diehl, U.S:
Patent 3,308,067, issued march 7, 1967.
Acrylic/maleic-based copolymers may also be used as a preferred
component of the dispersing/anti-redeposition agent. Such materials
include the water-soluble salts of copolymers of acrylic acid and
malefic acid. The average molecular weight of such copolymers in the
acid form preferably ranges from about 2,000 to 100,000, more
preferably from about 5,000 to 75,000, most preferably from about
7,000 to 65,000. The ratio of acrylate to maleate segments in such
copolymers will generally range from about 30:1 to about 1:1, more
preferably from about 10:1 to 2:1. Water-soluble salts of such acrylic
acid/maleic acid copolymers can include, for example, the alkali metal,
ammonium and substituted ammonium salts. Soluble acrylate/maleate
copolymers of this type are known materials which are described in
European Patent Application No. 66915, published December 15,
1982, as well as in EP 193,360, published September 3, 1986, which
also describes such polymers comprising hydroxypropylacryiate. Still
other useful dispersing agents include the maleic/acryiic/vinyl alcohol
terpolymers. Such materials are also disclosed in EP 193,360,
including, for example, the 45/45/10 terpolymer of
acrylic/maleic/vinyl alcohol.
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Chelating Agents
The detergent compositions herein may also optionally contain
one or more iron and/or manganese chelating agents. Such chelating
agents can be selected from the group consisting of amino .
carboxylates, amino phosphonates, polyfunctionally-substituted
aromatic chelating agents and mixtures therein, all as hereinafter
defined. Without intending to be bound by theory, it is believed that
the benefit of these materials is due in part to their exceptional ability
to remove iron and manganese ions from washing solutions by
formation of soluble chelates.
Amino carboxylates useful as optional chelating agents include
ethylenediaminetetracetates, N-hydroxyethylethylene
diaminetriacetates, nitrilotriacetates, ethylenediamine
tetraproprionates, triethylenetetraamine- hexacetates,
diethylenetriaminepentaacetates, and ethanoldiglycines, allcali metal,
ammonium, and substituted ammonium salts therein and mixtures
therein.
Amino phosphonates are also suitable for use as chelating agents
in the compositions of the invention when at least low levels of total
phosphorus are permitted in detergent compositions, and include
ethylenediaminetetrakis (methylenephosphonates) as DEQUEST
Preferred, these amino phosphonates to not contain alkyl or alkenyl
groups with more than about 6 carbon atoms.
Polyfunctionally-substituted aromatic chelating agents are also
useful in the compositions herein. See U.S. Patent 3,812,044, issued
May 21, 1974, to Connor et al. Preferred compounds of this type in
acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-
disulfobenzene.
A preferred biodegradable chelator for use herein is
ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as
described in U.S. Patent 4,704,233, November 3, 1987, to Hartman
and Perlcins.
Trade-mark
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If . utilised, these chelating agents will generally comprise from
about 0.1 % to about 10 % by weight of the detergent compositions
herein. More preferably, if utilised, the chelating agents will comprise
from about 0.1 % to about 3.0 % by weight of such compositions.
Enzymes
Enzymes can be included in the formulations herein for a wide
variety of fabric laundering purposes, including removal of protein-
based, carbohydrate-based, or triglyceride-based stains. The enzymes
to be incorporated include proteases, amylases, lipases, cellulases, and
peroxidases, as well as mixtures thereof. Other types of enzymes may
also be included. They may be of any suitable origin, such as
vegetable, animal, bacterial, fungal and yeast origin. However, their
choice is governed by several factors such as pH-activity and/or
stability optima, thermostability, stability versus active detergents,
builders and so on. In this respect bacterial or fungal enzymes are
preferred, such as bacterial amylases and proteases, and fungal
cellulases.
Enzymes are normally incorporated at levels sufficient to provide
up to about S mg by weight, more typically about 0.01 mg to about 3
mg, of active enzyme per gram of the composition. Stated otherwise,
the compositions herein will typically comprise from about 0.001 % to
about 10 % , preferably 0.01 % to 5 % by weight of a commercial
enzyme preparation. Protease enzymes are usually present in such
commercial preparations at levels sufficient to provide from 0.005 to
0.1 Anson units (AU) of activity per gram of composition.
Suitable examples of proteases are the subtilisins which are
obtained from particular strains of B. subtilis and B. licheniforms.
Another suitable protease is obtained from a strain of Bacillus, having
maximum activity throughout the pH range of 8-12, developed and
sold by Novo Industries A/S under the registered trade name
ESPERASE. The preparation of this enzyme and analogous enzymes is
described in British Patent Specification No. 1,243,784 of Novo.
Proteolytic enzymes suitable for removing protein-based stains that are
CA 02214842 2000-O1-13
16
commercially available include those sold under the tradenames
ALCALASE-~nd SAVINASE#by Novo Industries A/S (Denmark) and
MAXATASE-~y International Bio-Synthetics, Inc. (The Netherlands).
Other proteases include Protease A (see European Patent Application
130,756, published January 9, 1985) and Protease B (see
European Patent Application 130,756, Bott et al, published January 9,
1985).
Amylases include, for example, a-amylases described in British
Patent Specification No. 1,296,839 (Novo), RAPIDASE; International
Bio-Synthetics, Inc. and TERMAMYL, Novo Industries.
The cellulase usable in the present invention include both bacterial
or fungal cellulase. Preferably, they will have a pH optimum of
between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent
4,435,307, Barbesgoard et al, issued March 6, 1984, which discloses
fungal cellulase produced from Humicola insolens and Humicola strain
DSM1800 or a cellulase 212-producing fungus belonging to the genus
Aeromonas, and cellulase extracted from the hepatopancreas of a
marine mollusk (Dolabella Auricula Solander). Suitable cellulases are
also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-
2.247.832. CAREZYME~(Novo) is especially useful.
Suitable lipase enzymes for detergent usage include those
produced by microorganisms of the Pseudomonas group, such as
Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent
1,372,034. See also lipases in Japanese Patent Application 53,20487,
laid open to public inspection on February 24, 1978. This lipase is
available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under
the trade name Lipase P "Amano," hereinafter referred to as "Amano-
P." Other commercial lipases include Amano-CES,# lipases ex
Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum
NRRLB 3673, commercially available from Toyo Jozo Co., Tagata,
Japan; and further Chromobacter viscosum lipases from U.S.
Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and
lipases ex Pseudomonas gladioli. The LIPOLASE'' enzyme derived
# Trade-marks
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from Humicola lanuginosa and commercially available from Novo (see
also EPO 341,947) is a preferred lipase for use herein.
Peroxidase enzymes are used in combination with oxygen
sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide,
etc. They are used for "solution bleaching," i.e. to prevent transfer of
dyes or pigments removed from substrates during wash operations to
other substrates in the wash solution. Peroxidase enzymes are known
in the art, and include, for example, horseradish peroxidase, ligninase,
and haloperoxidase such as chloro- and bromo-peroxidase. Peroxidase-
containing detergent compositions are disclosed, for example, in PCT
International Application WO 89/099813, published October 19, 1989,
by O. Kirk, assigned to Novo Industries A/S.
A wide range of enzyme materials and means for their
incorporation into synthetic detergent compositions are also disclosed
in U.S. Patent 3,553,139, issued January 5, 1971 to McCarty et al.
Enzymes are further disclosed in U.S. Patent 4,101,457, Place et al,
issued July 18, 1978, and in U.S. Patent 4,507,219, Hughes, issued
March 26, 1985, both. Enzyme materials useful for liquid detergent
formulations, and their incorporation into such formulations, are
disclosed in U.S. Patent 4,261,868, Hora et al, issued April 14, 1981.
Enzymes for use in detergents can be stabilized by various techniques.
Enzyme stabilization techniques are disclosed and exemplified in U.S.
Patent 3,600,319, issued August 17, 1971 to Gedge, et al, and
European Patent Application Publication No. 0 199 405, Application
No. 86200586.5, published October 29, 1986, Venegas. Enzyme
stabilization systems are also described, for example, in U.S. Patent
3,519,570.
Enzyme Stabilizers
The enzymes employed herein are stabilized by the presence of
water-soluble sources of calcium and/or magnesium ions in the
finished compositions which provide such ions to the enzymes.
(Calcium ions are generally somewhat more effective than magnesium
ions and are preferred herein if only one type of cation is being used.)
CA 02214842 2000-O1-13
18
Additional stability can be provided by the presence of various other
art-disclosed stabilizers, especially borate species: see Severson, U.S.
4,537,706.
Bleaching Compoundc - Bleaching Ae~,d ~l~a~h A~t;~at r,
The detergent compositions herein may optionally contain
bleaching agents or bleaching compositions containing a bleaching
agent and one or more bleach activators. When present, bleaching
agents will typically be at levels of from about 0.196 to about 30 % ,
more typically from about 1 % to about 20%, of the detergent
composition, especially for fabric laundering. If present, the amount
of bleach activators will typically be from about 0.1 ~ to about 60%,
more typically from about 0.5 96 to about 4036 of the bleaching
composition comprising the bleaching agent-plus-bleach activator.
The bleaching agents used herein can be any of the bleaching
agents useful for detergent compositions in textile cleaning, hard
surface cleaning, or other gleaning purposes that are now known or
become known. These include oxygen bleaches as well as other
bleaching agents. Perborate bleaches, e.g., sodium perborate (e.g.,
mono- or tetra-hydrate) can be used herein.
Another category of bleaching agent that can be used without
restriction encompasses percarboxylic acid bleaching agents and salts
thereof. Suitable examples of this class of agents include magnesium
monoperoxyphthalate hexahydrate, the magnesium salt of metachloro
perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and
diperoxydodecanedioic acid. Such bleaching agents are disclosed in
U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S.
Patent 4,634,551, Burns et al. issued January 6, 1987, European
Patent Application 0,133,354, Banks et al, published February 20,
1985, and U.S. Patent 4,412,934, Chung et al, issued November 1,
1983. Highly preferred bleaching agents also include 6-nonylamino-6-
ozoperoxycaproic acid as described in U.S. Patent 4,634,551, issued
January 6, 1987 to Burns et al. .
CA 02214842 2000-O1-13
19
Peroxygen bleaching agents can also be used. Suitable peroxygen
bleaching compounds include sodium carbonate peroxyhydrate and
equivalent "percarbonate" bleaches, sodium pyrophosphate
peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate
bleach (e.g., OXONE; manufactured commercially by DuPont) can
also be used.
Mixtures of bleaching agents can also be used. Peroxygen
bleaching agents, the perborates, etc., are preferably combined with
bleach activators, which lead to the in situ production in aqueous
solution (i.e., during the washing process) of the peroxy acid
corresponding to the bleach activator. Various nonlimiting examples
of activators are disclosed in U.S. Patent 4,915,854, issued April 10,
1990 to Mao et al, and U.S. Patent 4,412,934. The
nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene
diamine (TAED) activators are typical, and mixtures thereof can also
be used. See also U.S. 4,634,551 for other typical bleaches and
activators useful herein.
Highly preferred amido-derived bleach activators are those of the
formulae:
R1N(R5)C(O)R2C(O)L or R1C(O)N(R5)R2C(O)L
wherein R1 is an alkyl group containing from about 6 to about 12
carbon atoms, R2 is as alkylene containing from 1 to about 6 carbon
atoms, RS is H or alkyl, aryl, or alkaryl containing from about 1 to
about 10 carbon atoms, and L is any suitable leaving group. A leaving
group is any group that is displaced from the bleach activator as a
consequence of the nucleophilic attack on the bleach activator by the
perhydrolysis anion. A preferred leaving group is phenyl sulfonate.
Preferred examples of bleach activators of the above formulae
include (6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamido-
caproyl)oxybenzenesulfonate, (6-decanamido-
caproyl)oxybenzenesulfonate, and mixtures thereof as described in
U.S. Patent 4,634,551.
Trade-mark
CA 02214842 2000-O1-13
20
Another class of bleach activators comprises the benzoxazin-type
activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued
October 30, 1990. A highly
preferred activator of the benzoxazin-type is:
O
II
C~0
C
''
N
Still another class of preferred bleach activators includes the acyl
lactam activators, especially acyl caprolactams and acyl valerolactams
of the formulae:
O
0
O C-CHZ-CHZ O C-CHZ-CHZ
Re~-~C~~HZ~CH~z Rg-C-N~ I
C H2-C HZ
wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group
containing from 1 to about 12 carbon atoms. Highly preferred lactam
activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-
trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl
caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl
valerolactam, decanoyl valerolactam, undecenoyl valerolactam,
nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and
mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson,
October 8, 1985, which discloses
acyl caprolactams, including benzoyl caprolactam, adsorbed into
sodium perborate.
Bleaching agents other than oxygen bleaching agents are also
known in the art and can be utilised herein. One type of non-oxygen
bleaching agent of particular interest includes photoactivated bleaching
agents such as the sulfonated zinc and/or aluminium phthalocyanines.
See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If
used, detergent compositions will typically contain from about 0.025
CA 02214842 2000-O1-13
21
to about 1.25%, by weight, of such bleaches, especially sulfonate zinc
phthalocyanine.
If desired, the bleaching compounds can be catalyzed by means of
a manganese compound. Such compounds are well known in the art
and include, for example, the manganese-based catalysts disclosed in
U.S. Pat. 5,246,621, U.S. Pat. 5,244,594; U.S. Pat. 5,194,416; U.S.
Pat. 5,114,606; and European Pat. App. Pub. Nos. 549,271 A 1,
549,272A 1, 544,440A2, and 544,490A 1; Preferred examples of these
catalysts include Mn~2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclo-
nonane~(PF6~, Mn~2(u-O) 1 (u-OAc~( 1,4,7-trimethyl-1,4, 7-
triazacyclononane~_(C104~, Mn~4(u-O)6(1,4,7-
triazacyclononane)4(C104)4, Mn~MnN4(u-O) 1 (u-OAc~_( 1,4,7-
trimethyl-1,4,7-triazacyclononane~(C104)3, MnN(1,4,7-trimethyl-
1,4,7-triazacyclononane~- (OCH3)3(PF6), and mixtures thereof. Other
metal-based bleach catalysts include those disclosed in U.S. Pat.
4,430,243 and U.S. Pat. 5,114,611. The use of manganese with
various complex ligaads to enhance bleaching is also reported in the
following United States Patents: 4,728,455; 5,284,944; 5,246,612;
5,256,779; 5,280,117; 5,274,147; 5,153,161; 5,227,084;
Corrosion inhibitor compound
The compositions may contain corrosion inhibitors preferably selected
from organic silver coating agents, particularly paraffin, nitrogen-
containing corrosion inhibitor compounds, bismuth compounds and
Mn(Il7 compounds, particularly Mn(In salts of organic ligands.
Organic silver coating agents are described in PCT Publication
No. W094/ 16047 and copending Canadian Patent Application No.
2,151,659 filed June 13, 1995. Nitrogen-containing corrosion
inhibitor compounds are disclosed in copending PCT Publication No.
W095/02680 published January 26, 1995. Mn(II) compounds for use
in corrosion inhibition are described in copending Canadian Patent
Application No. 2,144,103 filed March 7, 1995.
CA 02214842 1997-09-08
w0 96/28530 PCT/US96/02769
22
Organic silver coating agents
Organic silver coating agent may be incorporated at a level of
from 0.05 % to 10 % , preferably from 0.1 % to 5 % by weight of the
total composition.
The functional role of the silver coating agent is to form ' in use'
a protective coating layer on any silverware components of the
washload to which the compositions of the invention are being applied.
The silver coating agent should hence have a high affinity for
attachment to solid silver surfaces, particularly when present in as a
component of an aqueous washing and bleaching solution with which
the solid silver surfaces are being treated.
Suitable organic silver coating agents herein include fatty esters
of mono- or polyhydric alcohols having from 1 to about 40 carbon
atoms in the hydrocarbon chain.
The fatty acid portion of the fatty ester can be obtained from
mono- or poly-carboxylic acids having from 1 to about 40 carbon
atoms in the hydrocarbon chain. Suitable examples of monocarboxylic
fatty acids include behenic acid, stearic acid, oleic acid, palmitic acid,
myristic acid, lauric acid, acetic acid, propionic acid, butyric acid,
isobutyric acid, valeric acid, lactic acid, glycolic acid and (3,(3'-
dihydroxyisobutyric acid. Examples of suitable polycarboxylic acids
include: n-butyl-malonic acid, isocitric acid, citric acid, malefic acid,
malic acid and succinic acid.
The fatty alcohol radical in the fatty ester can be represented by
mono- or polyhydric alcohols having from 1 to 40 carbon atoms in the
hydrocarbon chain. Examples of suitable fatty alcohols include;
behenyl, arachidyl, cocoyl, oleoyl and lauryl alcohol, ethylene glycol,
glycerol, ethanol, isopropanol, vinyl alcohol, diglycerol, xylitol,
sucrose, erythritol, pentaerythritol, sorbitol or_ sorbitan.
CA 02214842 1997-09-08
wo 96i2ss3o PCTlUS96102769
23
Preferably, the fatty acid and/or fatty alcohol group of the fatty
ester adjunct material have from 1 to 24 carbon atoms in the alkyl
chain.
Preferred fatty esters herein are ethylene glycol, glycerol and
sorbitan esters wherein the fatty acid portion of the ester normally
comprises a species selected from behenic acid, stearic acid, oleic
acid, palmitic acid or myristic acid.
The glycerol esters are also highly preferred. These are the
mono-, di- or tri-esters of glycerol and the .fatty acids as defined above.
Specific examples of fatty alcohol esters for use herein include:
stearyl acetate, palmityl di-lactate, cocoyl isobutyrate, oleyl maleate;
oleoyl dimaleate , and tallowyl proprionate. Fatty acid esters useful
herein include: xylitol monopalmitate, pentaerythritol monostearate,
sucrose monostearate, glycerol monostearate, ethylene glycol
monostearate, sorbitan esters. Suitable sorbitan esters include sorbitan
monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan
monomyristate, sorbitan monobehenate, sorbitan mono-oleate, sorbitan
dilaurate, sorbitan distearate, sorbitan dibehenate, sorbitan dioleate,
and also mixed tallowalkyl sorbitan mono- and di-esters.
Glycerol monostearate, glycerol mono-oleate, glycerol
monopalmitate, glycerol monobehenate, and glycerol distearate are
preferred glycerol esters herein.
Suitable organic silver coating agents include triglycerides,
mono or diglycerides, and wholly or partially hydrogenated derivatives
thereof, and any mixtures thereof. Suitable sources of fatty acid esters
include vegetable and fish oils and animal fats. Suitable vegetable oils
include soy bean oil, cotton seed oil, castor oil, olive oil, peanut oil,
safflower oil, sunflower oil, rapeseed oil, grapeseed oil, palm oil and
corn oil.
Waxes, including microcrystalline waxes are suitable organic
silver coating agents herein. Preferred waxes have a melting point in
CA 02214842 2000-O1-13
24
the range from about 35°C to about 110°C and comprise generally
from 12 to 70 carbon atoms. Preferred are petroleum waxes of the
paraffin and microcrystalline type which are composed of long-chain
saturated hydrocarbon compounds.
Alginates and gelatin are suitable organic silver coating agents
herein.
Dialkyl amine oxides such as C 12-C20 methylamine oxide, and
dialkyl quaternary ammonium compounds and salts, such as the C 12-
C2p methylammonium halides are also suitable.
Other suitable organic silver coating agents include certain
polymeric materials. Polyvinylpyrrolidones with an average molecular
weight of from 12,000 to 700,000, polyethylene glycols (PEG) with an
average molecular weight of from 600 to 10,000, polyamine N-oxide
polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,
and cellulose derivatives such as methylcellulose,
carboxymethylcellulose and hydroxyethylcellulose are examples of
such polymeric materials.
Certain perfume materials, particularly those demonstrating a
high substantivity for metallic surfaces, are also useful as the organic
silver coating agents herein.
A wide variety of other ingredients useful in detergent
compositions can be included in the compositions herein, including
other active ingredients, carriers, hydrotropes, processing aids, dyes
or pigments, etc. If desired, soluble magnesium salts such as MgCl2,
MgS04, and the like, can be added at levels of, typically, 0.1 %-2 % ,
to provide enhanced grease removal performance. Ingredients may
also be incorporated to assist in the tabletting process such as
lubricating agents, sodium acetate and nonionic surfactants.
CA 02214842 2000-O1-13
25
Tablet Preparation
Another aspect of the present invention relates to the preparation
of the tabletted detergent composition. The tablet may be manufactured
using any suitable compacting process, such as tabletting, briquetting
or extrusion, preferably tabletting. Preferably the tablets are
manufactured using a standard rotary tabletting press (such as Courtoy
RS) using compression forces of from 5 to 13KN/cm2, more
preferably from 5 to 11KN/cm2.
According to the present invention the tablets are prepared by dry
mixing the not fully hydrated builder/filler system, optional ingredients
selected from polymeric polycarboxylates, chelants, bleach and bleach
activator and then adding water and optionally other ingredients which
may be sprayed on such as nonionic surfactants, chelants and
silvercare additives. Prior to compaction any additional sensitive
ingredients such as enzymes, dyes and perfumes are dry mixed.
The composition is then tabletted by convensional means, on a 12
head rotary press under a compression force of 5-13KN/cm2 so that
the tablet has a minimum hardness of 176N to 245N, preferably from
195N to 275N, measured by a C 100 hardness test as supplied by I.
Holland Instruments. These processes may be used to prepare
homogenous or layered tablets of any size or shape. Preferably the
tablets are symmetrical to ensure the uniform dissolution of the tablet
in the wash liquor.
According to the present invention said tabletted detergent
composition may find utility in all types of automatic dish- and laundry
washing machines including industrial and domestic.
Ln the detergent compositions, the abbreviated component
identifications have the following meanings:
CA 02214842 1997-09-08
WO 96!28530 PCT/US96/02769
26
35EY : A mixture of C 13-15 Predominantly linear
primary alcohol condensed with an average
of
2 and 6 moles of ethylene oxide
Silicate : Sodium Silicate (Si02:Na20 ratio = 2.0)
Sulphate : Anhydrous sodium sulphate
AA : Homopolymer of acrylic acid, average
molecular weight about 8,000.
Citrate : Tri-sodium citrate dihydrate
DETPMP : Diethylene triamine penta (Methylene
phosphoric acid), marketed by Monsanto
under
the Tradename bequest 2060
TAED : Tetraacetyl ethylene diamine
Perborate ~ Anhydrous sodium perborate monohydrate
:
bleach
Paraffin : Paraffin oil sold under the tradename
Winog 70
b Wintershall
CA 02214842 1997-09-08
WO 96/28530 PCT/US96I02769
27
Example
The following tabletted detergent compositions suitable for use in
an automatic dishwashing machine were prepared as described. The
' tablet were prepared by dry mixing all of the components except
HEDP, Benzotrioazole, para~n, enzymes and the added water. The
HEDP, benzotriazole, para~n, nonionic surfactant and water are then
sprayed on and the composition mixed. The enzymes and additional
sensitive ingredients are then added prior to compression to produce a
25g tablet.
Tablet Ref I II III
Citrate 25 25 33 26.4
3.2 3.2 4 3.2
Silicate 26.4 26.4 33 26.4
HEDP 0.66 0.66 0.83 0.66
PB 1 1.56 1.56 1.95 1.56
PB4 6.92 6.92 8.65 6.91
TAED 4.36 4.36 5.45 4.36
Enz mes 3 3 3.8 3
Silvercare 0.64 0.64 0.8 0.6
additive
35EY 1.2 1.2 1.5 1.2
Sul hate 23 22 - 1.95
Added Water 0 0.5 0.7 1.0
Misc. Balance to 100
Total water 11.8 12.3 12.5 12.8
content
Equilibrium 28.6 28.8 31.4 30.9
relative humidity
at 26C
av. Hardness 144N 239N ~ 221N 220N
